JPH01188512A - Polyurethane or polyurea containing phenol as terminal group and epoxide resin containing the same - Google Patents

Abstract

PURPOSE: To obtain a novel compound which is easily miscible with epoxy resin and gives water-proof flexible cured material as a hardener of epoxy resin by the reaction of a specific elastomer prepolymer and a polyphenol.

CONSTITUTION: This compound is water-soluble and expressed by the formula I (m=1, 2; n=2-6; R¹=n valent group after removing terminal NCO group or amino group from a soluble or dispersible elastomer prepolymer for epoxide resin; R²=H, 1-6C alkyl; R³ = phenolic hydroxyl, m+1 valent group of polyphenol after removing amino group; X=O, NR²). This compound is obtained by the reaction of polyisocyanate of the formula II and polyphenol or aminophenol of the formula III. The compound of the formula II is preferably the additive of hydroxyl terminated polyether or polyester and diisocyanate.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention provides novel phenol-terminated polyurethanes and polyureas, epoxide resins and curable mixtures containing these compounds, and softeners for epoxide resin reservoirs. It concerns the use of these compounds as adhesives as well as the use of curable mixtures as adhesives.

[Conventional technology]

Key with phenol? stubbed (phenol-ca)
ped) Polyurethane is DE-A 2,152,606
Disclosed in the issue. The conventionally known compounds are obtained by reacting prevo-limer diisocyanates with substituted or unsubstituted monophenols. The product no longer contains free phenolic hydroxyl groups. The compounds are combined with epoxide resins and polyamine hardeners to provide curable coatings that are particularly characterized by elasticity.

[Problem to be solved by the invention]

A mixture containing the reaction product of isocyanate-terminated butadiene-isoprene oligomers and chlorine-containing bisphenols is known from 8U-A 857,156.

These mixtures are used as intermediates for the production of polyesters and generally they contain excess amounts of bisphenols. The butadiene-isoprene oligomers used are not reasonably compatible with the epoxide resins.

Water-soluble or partially water-soluble phenol-terminated polyurethanes derived from water-soluble or partially water-soluble polyalkylene glycols, diisocyanates and bisphenols are disclosed in US Pat. No. 4,423,201. These compounds, when reacted with epoxide resins and phenols, give water-dispersible epoxide resins. Modified epoxide resins can be used as coatings. Due to their high content of hydrophilic groups, cured products tend to absorb water and swell when stored in water.

Thermoplastic adhesives obtained by reacting prepolymer isocyanates derived from polyalkylene glycols with substantially stoichiometric amounts of cycloaliphatic or aromatic diols are disclosed in FR-AI, No. 526.963. ing. The compounds are substantially linear and have high molecular weights; they can be used as hot melt adhesives. Due to their high molecular weight, these compounds are either insoluble in epoxide resins or give rise to highly viscous products with a tendency to solidify. Phenol-masked prepolymers are not described.

The combination of aromatic polyols and polyfunctional isocyanates is disclosed in US-& 4,396,647. These mixtures contain no free phenolic hydroxyl groups and can be cured by gas treatment with tertiary amines to give entirely insoluble crosslinked products. Paints can be produced from mixtures.

Storage-stable epoxide compositions containing polyisocyanates blocked with monophenols or polyphenols are disclosed in US Pat. No. 3,442,974. Phenol-capped polyisocyanates with elastic properties are not described.

Finally, polyurethanes derived from the reaction of polyisocyanates with polyphenols are FR 41,518,54
It is disclosed in No. 6. The products either have high softening points and high molecular weights, or they are isocyanate-terminated polyurethanes that can be crosslinked via the isocyanate groups by the action of moisture. The compound is suitable for use as a lacquer.

Selected prepolymers, phenol-capped polyurethanes and polyureas that are easily miscible with epoxide resins, can be crosslinked with epoxide resins via phenolic hydroxyl groups, and result in products with good resistance to water. The older brother was sent away. These polyurethanes or polyureas give the cured epoxide resins good flexibility, high peel strength and very good adhesion to metals, especially oil-coated pieces.

[Failure to solve the problem]

The present invention is based on the following formula I: (wherein m represents 1 or 2, n represents 2 to 6, and R1 is a terminal isocyanate group or amine group from an elastomer prepolymer that is soluble or dispersible in an epoxide resin) R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, R8 represents a phenolic hydroxyl group, and optionally a polyphenol after removing an amine group. or m + represents a monovalent group of aminephenol, and X represents a group represented by 10- or -NR2-.

).

Within the scope of this specification, "water-insoluble compounds" are defined as 5% by weight
Up to 11.5% by weight, preferably up to 11.5% by weight, and when stored in water a small amount of water, preferably up to 5% by weight.
This is to be understood as meaning a compound which absorbs less than % by weight of water, in particular less than 0.5% by weight, or which swells only slightly under these circumstances.

Within the scope of this specification, [elastomer prepolymer group R
IJ is terminated with an n-isocyanate group or an n-amino group and, after the groups have been capped, is combined with an epoxide resin to yield a compound of formula I that provides an elastomeric phase after curing. It should be understood as meaning a group of prepolymers. The combination can be a homogeneous or heterogeneous combination with epoxide resins. Generally, elastomeric phases are characterized by a glass transition temperature below 0°C.

Within the scope of this specification, a "prepolymer that is soluble or dispersible in an epoxide resin" is defined as a prepolymer that is terminated with n-isocyanate or n-amine groups and, after these groups have been masked, is added to the epoxide resin. A prepolymer which, when combined with an epoxide resin, does not result in macroscopic separation of the two components; is to be understood as meaning a group of.

In the case of heterogeneous systems, the change in the solubility parameters of the two components should be between (12 and 1.0, preferably between 0.2 and cL60).
B, Booknall (C, B.

Bucknall), [Toughened Plastics J
, Chapter 2, Applied Science Publishers, Inc.
hers Ltd, ), o/ton 1977
Listed in the year.

Generally, the prepolymer on which R' is based has a molecular weight (number average) of from 150 to 1oooo, preferably from 1500 to 6000.

The average functionality of these prepolymers is at least 2, preferably 2 to 3, and particularly preferably 2 to 2.
．． It is 5.

zo is preferably a methyl group, but especially a hydrogen atom.

Depending on the nature of the prepolymer on which R+ is based, compounds of formula I can be prepared by different routes.

In the case of prepolymer isocyanates, they are compounds of the formula (a): R1-←NCO)n(Ila); ) can be produced by reacting with a polyphenol or an amine phenol (process a); a polyurea of formula I can also be produced by reaction with a polyurea of the following formula b: R1-+
-NR2H)n(■b) It can also be obtained by reacting the compound represented by the following formula (■b) with a urethane represented by the following formula (process b); L# A compound represented by the formula I having a very phenol group or an aminephenol group.
The compound represented by (■b) can also be produced by reacting with a cyclic carbonate or urethane represented by the following formula (■c) (Process C).

The above formula (la, [b, lia, ilb and l
In lc, base ul, u! , R8 and X and the indices m and n have the meanings defined above in this specification; represents an alkyl group or a [engineering group], and R"
has one of the meanings given to % R'' and the group -0
- and -X- each represent a divalent carbocyclic aromatic group located in the ortho or peristal position to each other.

Generally, the group t is derived from a phenol or an amine phenol having a mononuclear or polynuclear carbocyclic aromatic group.

Phenolic or aminophenol groups with various carbocyclic aromatic groups can be fused or linked via a suitable bridge.

Examples of phenols or amine phenols with fused groups are dihydroquinaphthalene or dihydroxyanthracene or aminonaphthol.

Preferably, the group R8 has the following formula: (wherein, Z directly represents a C-C bond, or
, -o-, -s-, -so, -, -co-, -coo-
.

represents a bridge selected from the group consisting of -CONR'- and -8IR9R10-, where R4 and t independently have 1 to 2 carbon atoms;
0 alkyl group, C2-C6 alkenyl group, C2-6 alkynyl group or halogen atom, p and q each independently represent Q, 1 or Vi2, R@, R? and R8 are each independently a hydrogen atom,
-cH or an alkyl group of 1 to C atoms, or R6 and R7 together with a common carbon atom form a cycloaliphatic group having 5 to 12 ring carbon atoms, and t and R'6 represents an alkyl group having 1 to 2 carbon atoms. ) is derived from bisphenol represented by Particularly preferred groups Ua are from the compounds of the formula (2) in which the hydroxyl group is bonded at the 4,4' position in the above formula (1): in particular, derivatives in which p and q represent 1 and R4 and t represent an allyl group. derived from.

Other particularly preferred groups are Z-CH2 in the above formula (1).
-, -C(CFI)2, 0-, -8Ox-1 direct C-〇 bond and especially -C(CH8)! p and qVi each represent 0 or 1, and R4 and t represent a C1-C6 alkyl group, a C2-C6 alkenyl group, especially allyl; or a C2 -C6 alkynyl group, in particular a glopargyl group, derived from subbisphenol.

Other preferred groups R8 are derived from mononuclear aminophenols, such as 2-93- or 4-aminephenols.

Other preferred radicals R''U are derived from mononuclear polyphenols such as resorcinol, hydroquinone or pyrogallol.

Particularly preferred groups R1 are derived from bisphenols, examples of which include 4,4'-dihydroxybiphenyl, bis-
(4-hydroxyphenyl)ether, bis-(4-hydroxyphenyl)sulfone, bis-(4-hydroxyphenyl)methane and 2,2-his-(4-hydroxyphenyl)furopane and the corresponding 3 of these compounds, 3'-dimethyl, 3,3'-dinonyl, 3,3'-
diallyl, s, t-dichloro, 6,3'-dibromo and s, 3', s.

It is a 5-tetrabromo derivative.

C1-C20 alkyl group R4-strapping Rs
is a linear or branched group.

Examples of these are methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, 2-ethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group , n-decyl group % n-undecyl group, n-dodecyl group, n-tetradecyl group, n
-hexadecyl group, n-octadecyl group or n-eicosyl group.

R4 and t are preferably C1 -C alkyl, particularly preferably C1 -C linear alkyl and very particularly preferably methyl.

C1 -C6 alkyl radicals of all kinds are preferably linear radicals, ie methyl, ethyl, n-propyl, n-butyl, n-pentyl or still Fin-hexyl; However, very preferred is the methyl group.

Examples of W and R6 as C2-C6 alknyl groups include vinyl group, allyl group, 1-propenyl group,
They are 1-butenyl group, 1-pentenyl group or 1-hexenyl group. Vinyl, 1-propenyl and allyl groups are preferred, and allyl group is very particularly preferred.

Examples of R4 and t as C2 -C6 alkynyl are ethynyl, propargyl, 1-butynyl, 1-pentenyl or 1-hexynyl. A propargyl group is preferred.

R4 and W as halogen atoms can be fluorine, chlorine, bromine or iodine.

A chlorine atom or a bromine atom is preferred. When strong adhesion to oil-coated steel is required, it is preferred to use compounds of formula (3) containing alkyl or alkenyl substituents. - In general, halogenated compounds of formula (1) increase flame retardancy.

If R6 and R7 together with a common carbon atom form an alicyclic group, this is, for example, a cyclopentylidene, cyclohexylidene, cyclooctylidene, cyclooctylidene or cyclododecylidene group. It is.

Cyclohexylyzo7 group or cyclododecylidene group is preferred.

The isocyanate of formula 1a can be used as a l) to or to brepolymer polyhydroxyl or polysulfhydryl compounds, optionally in combination with chain extenders (short-chain polyhydroxyl, polysulfhydryl or polyamine compounds). R2) a prepolymer component derived from an adduct of a polyisocyanate, preferably a diisocyanate or a triisocyanate and particularly preferably a diisocyanate, to a mixture of prepolymer components such as R2) a prepolymer polyamine, preferably derived from a prepolymer polyether amine; This is one of the prepolymer polyisocyanates produced.

The prepolymer component for the preparation of al) can be a condensation or addition polymer which may optionally contain 1-olefins grafted thereon, said 1-olefins containing not only non-polar groups; It is also possible to contain polar groups, such as nitrile groups, ester groups or amide groups.

Examples of such polymers are polyesters, polyethers, polythioethers, polyacetals, polyamides, polyester-amides, polyurethanes, polyureas, alkyd resins, polycarbonates or polysiloxanes, if these compounds are hydroxyl-terminated or sulfhydryl-terminated. If group-terminated, it results in compounds of formula I that are insoluble in water and soluble or dispersible in epoxide resins, and these resins have elastic properties as described above. . Preference is given to polyethers or fragmented prepolymers with polyether fragments, such as polyether-amides, polyether-urethanes or polyether-ureas.

These compounds are known to those skilled in the art of polyurethane chemistry as components of polyurethane synthesis stocks. They may be linear or branched, with linear types being preferred.

Preferred components U for the synthesis of prepolymers polyisocyanates a1) are hydroxyl-terminated prepolymers having an average molecular weight (number average) of 150-10 000, very preferably 1500-3000.

In addition to the hydroxyl-terminated or sulfhydryl-terminated prepolymers, chain extenders can also be present for the preparation of the prepolymer polyisocyanates a1).

Monomers of this type are preferably difunctional or Vi3
It is sensory value.

If penta- or polyfunctional hydroxyl-terminated or sulfhydryl-terminated prepolymers or trifunctional or polyfunctional chain extenders are used for the preparation of component a1), the components for the synthesis are prepared in an organic solvent. The choice should be made such that an adduct a1) is formed which is soluble in or at least swellable.

If polyfunctional components for the synthesis are used, the degree of crosslinking can be adjusted in a manner known per se depending on the nature and proportions of these components.

Thus, if a difunctional prepolymer and a trifunctional or polyfunctional chain extender are used, generally only a low proportion of the polyfunctional component will be used, whereas the
When functional and hexafunctional or multifunctional prepolymers are combined, generally large amounts of multifunctional chain extenders can be present without excessive crosslinking. The degree of crosslinking will also depend on the functionality of the polyisocyanate. Thus, diisocyanates are generally used when trifunctional or multifunctional, hydroxyl-terminated or sulfhydryl-terminated components are present for synthesis, whereas diisocyanates are generally used for synthesis when difunctional hydroxyl-terminated or sulfhydryl-terminated components are present. If group-terminated components are used, polyfunctional isocyanates may also be used. Examples of preliminary prepolymer components for the preparation of polyisocyanates a1) are hydroxyl-terminated polyethers.

These can be prepared by nonionic polymerization, copolymerization or block copolymerization of alkylene oxides such as propylene oxide or butylene oxide, difunctional or polyfunctionalized alcohols such as monomers as initiator components.
．． 4-butanediol, 111,1-trimethylolethane, 1.1.1-)limethylolpropane, 1.2.
6-hexanediol, chrycerol, pentaerythritol or nlupitol are used, or amines such as methylamine, ethylenediamine or 1,6-
Glycols that can be subjected to polycondensation using hexanediol or by cationic polymerization or copolymerization of cyclic ethers such as tetrahydrofuran or propylene oxide, using acid catalysts such as Br3 etherate, or with elimination of decoupled water. Examples include polyalkylene ether-polyols obtained by polyJ condensation of 1,6-hexanediol in the presence of acid etherification catalysts such as p-toluenesulfonic acid. It is also possible to use oxaalkylation products of phosphoric acid or phosphorous acid with propylene oxide, butylene oxide or styrene oxide. These polyalkylene ether-polyols may also contain a low proportion of ethylene glycol units, as long as the insolubility of the compound of formula I in water is thereby maintained.

Other preferred hydroxyl-terminated polyethers contain 1-olefins grafted thereon, such as acrylonitrile, methyl/or acrylic esters. In this case, the weight proportion of the kraft component is generally 10-50%, especially 10-30%, relative to the amount of polymer used.
It is.

Other examples of prepolymer components for the production of polyisocyanates a1) are hydroxyl-terminated polyester polyols derived from dicarboxylic and/or polycarboxylic acids and diols and/or spanning polymers, preferably from dicarboxylic acids and diols. It is.

Examples of such polycondensates are adipic acid, sebacic acid, azelaic acid, dimeric and trimer fatty acids, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid and propylene glycol. , 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, diptylene glycol, tributylene glycol, tetrabutylene glycol, 2,2-dimethylpropane-1゜3 -diol, 1', 1.1-
It is a hydroxyl group-terminated polyester that can be produced from a polycondensate of trimethylolpropane, 1,1,1-trimethylolethane and 1,2,6-hexa/triol. Other suitable prepolymer synthesis components for the preparation of polyisocyanates a1) are other hydroxyl-terminated prepolymers, especially polyesters, for the formation of prepolymers that are soluble or dispersible in epoxide resins. Hydroxyl-terminated polybutadiene used with ethers.

Further examples of suitable prepolymer synthesis components for the production of polyisocyanates a1) are hydroxyl-terminated polycarbonates of the aforementioned diols or polyols; or amino alcohols such as ethanolamine, which can be prepared with the additional use of amino alcohols such as ethanolamine. Polyester-amide:
or polyalkylenethioether-polyols, such as thiodiglycol and itself and diols and/or
or polycondensation products with polyols such as 1,6-hexanediol, triethylene glycol, 2'2-dimethyl-1,3-propanediol or 1,1,1-trimethylolpropane; or polyacetals such as formaldehyde and diols and / or polycondensation products formed from polyols, such as 1,4-butanediol, 1,6-hexa/diol, thiodiglycol or 1,1,1-trimethylolpropane.

Preferred prepolymer synthesis components for the preparation of polyisocyanates a1) are hydroxyl-terminated polyesters or polyethers.

Other preferred prepolymer synthesis components for the preparation of polyisocyanates a1) are hydroxyl-terminated polybutadiene and hydroxyl-terminated polyalkylene glycols, especially polybutylene glycols, or hydroxyl-terminated polyalkylene glycols, especially 1 grafted thereon. - mixtures of polybutylene glycols containing olefins, especially styrene or acrylic acid derivatives such as acrylic esters or acrylonitrile.

Very particularly preferred prepolymer synthesis components for the preparation of polyisocyanates a1) are polyhydroxyl-terminated polyethers, in particular hydroxyl-terminated polyalkylene glycols.

Chain extenders for the preparation of prepolymer polyisocyanates a1) are known per se. Examples of these are the diols and polyols mentioned hereinabove for the production of hydroxyl-terminated polyethers, in particular the diols and polyols, especially trimethylolpropane or diamines such as diaminoethane, 1,6-diamithexane, piperazine. , 2,5-dimethylpiperazine, 1-amino-6-aminomethyl-5,5,5-trimethylcyclohexane, 4°4'-diaminocyclohexylmethane, 1,4-diaminocyclohexane and 1
．． 2-propylene diamine, or hydrazine, the amino acid hydrazine, the hydrazide, bis-hydrazide and bis-semicarbazide of semicarbazide carboxylic acids.

Short chain diols or triols are preferably used as chain extenders.

Prepolymer polyisocyanate a2) C. Prepolymer polyisocyanate a2) C. Prepolymers of the formula 11b, in particular amine-terminated polyethers, can be prepared by reaction with phosgene or polyisocyanates, preferably diisocyanates or triisocyanates, particularly preferably diisocyanates. It can be manufactured by a method known per se.

In addition to amine groups, amine group-terminated prepolymers generally do not contain other groups with active hydrogen atoms. Prepolymers with terminal amine groups are derived from the hydroxyl-terminated condensation or addition polymers mentioned herein above as synthesis components of general trap component a1) and from polyethers.

They are prepared by reacting said condensation or addition polymers containing secondary hydroxyl groups with ammonia and by reacting said condensation or addition polymers containing primary hydroxyl groups, such as polybutylene glycol, with acrylonitrile, and subsequently reacting these products. It can be produced by hydrogenating.

Prepolymer amino-terminated poly-THF is also used to terminate the divalent, still active, cationic THF polymer with potassium cyanate.

Sumiy, (S, Sm1th) etc., Macrom
ol, Sci, (:'hem.

It can be produced by the method described in J. M. C., 1399-1413 (1973).

The polyisocyanates used for the preparation of component a1) or a2) are generally aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, triisocyanates or tetraisocyanates or precursors which can be converted into isocyanates of this type. It is the body.

Aliphatic, cycloaliphatic or araliphatic diisocyanates or triisocyanates are preferred, aliphatic or cycloaliphatic diisocyanates being particularly preferred.

Preferred aliphatic diisocyanates are generally linear or branched α,ω-diisocyanates.

The alkylene chain may optionally be interrupted by oxygen or sulfur atoms and may optionally contain ethylenically unsaturated bonds.

Preference is given to α,ω-diisocyanates having linear saturated alkylene groups having 2 to 20 carbon atoms.

Examples of such groups are ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene. , octadecamethylene group and eicosamethylene group.

Preferred aliphatic α interrupted by a foreign atom.

Examples of ω-diisocyanate groups are -(CH, -CH2-
Q).

-CHz-CHt-, -(CH(CHs)-CHz-0
':l. -CH(CHs)-CHr.

-(CH2-CH, -CH, -CH, -0) -CH,
-CH, -CH, -G(, -O and -(CH2-CH,
-S) -CH2-CH2- (in the above formula, 0 represents 1 to 20).

Preferred cycloaliphatic diisocyanates are generally derivatives derived from substituted or unsubstituted cyclopentane, cyclohexane or cycloheptane. It is also possible for two such rings to be joined to each other via a bridge.

Examples of groups of this type are 1,3-cyclohexylene, 1,
4-cyclohexylene or dodecahydrodiphenylmethane-4,4'-diyl.

It is also possible to use diisocyanates or triisocyanates derived from dimeric or trimer fatty acids. These compounds can be obtained in a manner known per se from fatty acids by rearrangement to the corresponding diisocyanates or triisocyanates (Curtius, Rose/or Hofmann rearrangement).

Examples of preferable aromatic diisocyanates include -〇H among the more divalent phenol groups mentioned above in this specification.
This corresponds to an example in which the group is substituted with a -NCO group.

Examples of araliphatic diisocyanate groups are 1,2-xylylene and 1,4-xylylene. Particular examples of suitable polyisocyanates are 2,4-diycyanatotoluene and their technical mixtures with 2,6-diycyanatotoluene, 2,6-diycyanatotoluene, 1,5-diycyanatotoluene, isocyanatonaphthalene, 4,4'-diisocyanatodiphenylmethane and various diisocyanatodiphenylmethanes (e.g. 4,4'- and 2.4'-diisocyanatodiphenylmethane).
'-isomer), urethanized 4゜4'-diyne cyanatodiphenyl-methane, carbodiimidized 4
．． 4-diynecyanatodiphenylmethane, uretdione of 2,4-diynecyanatotoluene, triisocyanatotriphenylmethane, adduct formed from diynecyanatotoluene and trimethylolpropane, trimer formed from diynecyanatotoluene , diisocyanato-m-xylene, N,N-di(4-methyl-3-incyanatophenyl)-urea, mixed trimer product of diisocyanatotoluene and 1,6-diisocyanatohexamethylene, 1,6-di Isocyanatohexane, 3,5
．． 5-) Dimethyl-1-incyanato-3-isocyanatomethylcyclohexane (inphorone diisocyanate), N,N,N-tri(6-indianatohexyl)
-piureto, 2.2.4-trimethyl-1,6-diisocyanatohexane, 1-methyl-2,4-diisocyanatocyclohexane, dimeryl diisocyanate, 4.4
'-diynecyanatodicyclohexylmethane, trimer isophorone diisocyanate, trimer hexane diisocyanate and methyl 2,6-diisocyanatohexanoate.

Component a1)4 or a2) is prepared in a manner known per se by reacting a hydroxyl-terminated, sulfhydryl-terminated or amine-terminated prepolymer component with a polyisocyanate or a mixture of these components. The reaction optionally includes a chain extender, i.e., a monomer,
It may also be carried out in the presence of difunctional or polyfunctional components.

The preparation of components a1) and also t/'1a2) is carried out without a solvent or in a solvent that is inert towards isocyanates.

Examples of inert solvents are esters, such as ethyl acetate, butyl acetate, methyl glycol acetate or ethyl acetate; ketones, such as methyl, ethyl ketone or methyl isobutyl ketone; aromatic compounds, such as toluene or xylene, or halogenated hydrocarbons, e.g. Trichloroethane or methylene dichloride.

Urethane may also be present in prepolymers containing hydroxyl groups, sulfhydryl groups or amino groups, if some additional chain lengthening reaction via the urea group is acceptable or even desirable. Good monomer t5-2.5 preferably B 1-8-2.2 o
NC010H Straddling NCO/SH Straddling NCO/NH
z ratio of diisocyanate or polyisocyanate, if appropriate initially at 0-25°C and with cooling and subsequently optionally preferably 5O
-12 (react by heating to 1°C for several hours.

If chain lengthening reactions are not desired, generally a substantially large excess of diisocyanate or polyisocyanate is used, e.g. 3-5 NC010H.

NCO/SH is still used in NCO/NH, and no chain extender is used, and the operation is performed at a low ratio of NCO1
0H, NCO/SH or NCO/NH2. After the reaction, excess diisocyanate or polyisocyanate is optionally removed, for example by thin film distillation or solvent extraction.

The reaction of the hydroxyl-terminated, sulfhydryl-terminated or amide-7-terminated prepolymer with the polyisocyanate is carried out in the presence of catalysts which are known per se.

Examples of these are diazabicyclooctane, dibutyltin dilaurate or tin(II) octoate. These catalysts are used in customary amounts, for example in amounts of 0.001-2% by weight, based on the amount of polyisocyanate.

The reaction between component a1) i or a2) (polyisocyanate ■a) and phenol or aminephenol ■a is similar to the reaction described above between a hydroxyl-terminated, sulfhydryl-terminated or amine-terminated synthetic component and polyisocyanate. It will be held in

The polyphenol or amine phenol 1a is preferably used in this reaction so that the free NCO groups are substantially consumed by the reaction and the majority have one OH group or NH
2 is initially taken in such an amount that it reacts per polyphenol or amine phenol.

This will generally be the case if about 2 to 3 moles of OH groups of bisphenols or trisphenols or about 1 mole of NHz groups of aminophenols are initially taken up per mole of free isocyanate groups. polyphenol l
l[a, the OH:NCO ratio is generally 1.5:1.0
The ratio is 1.8:1.0 to 2.5:1.0, and the ratio is 1.8:1.0 to 2.5:1.0. In the case of amine phenol, N
H2: NCO,tt is generally 0.8:1.0 to 1
．． 2:1.0, preferably [18:1.0 to 1.0
:1.0. It is of course possible to use an excess of component In a, in which case chain lengthening can occur via the phenol, but the final product generally contains 50% of unreacted component 111a relative to the total mixture. It does not contain more than 0% by weight, and preferably does not contain more than 0% by weight.

In the case of the amine phenol IIIa, stoichiometric amounts are generally desirable.

It is also possible to use mixtures of phenols and/or amines phenols 11'[a for masking polyisocyanates [ai]. These mixtures can also still contain small amounts of monophenols. In this variant, the content of monophenols is selected such that the reaction product consists primarily of compounds of formula I having free phenolic OH groups.

The amine-terminated prepolymers in processes b) and C) are generally those already described in process a) and in which the polymeric polyisocyanate component ■
This is the prepolymer polyamine used for the production of a. A preferred compound (b) is an amine group-terminated polyether as described above. Urethane mbh following formula: HR”N
-R"-(OH)m (wherein R2, R8 and m have the above meanings).Urethane Ilb is derived from the aminophenol represented by R"-0-Co- CA, and is produced by capping it by a method known per se. In this formula R'' has the meaning defined earlier in the specification. Reaction of components Jib and 1llb (process b) Vi, two components in stoichiometric ratio or a slight excess of component 11Jb
This is generally done by first taking a sample of the compound of formula [b] and heating the mixture so that almost all free amine groups of the compound of formula [b are masked.

This reaction is preferably carried out in an inert solvent.

Examples of these have been described earlier herein.

Cyclic carbonate or llc has the following formula: HO-
Ortho- or berry-bisphenols represented by R12-OH or HR2N-R12-OH are also derived from amine phenols. R2 and R" in these formulas have the meanings previously defined herein. Component 111c can be prepared from these by reaction with phosgene. The reaction of components 11b and 1llc (process C) This is generally carried out by dividing the two components in the ratio or by first taking a slight excess of component 1 [c. In other aspects, the reaction is carried out in process a)
This is done as described in .

The molecular weight (number average) tri of the polyurethane or polyurea according to the present invention is usually 500 to 20,000, preferably q
It is within the range of 500 to 3000.

The viscosity of these compounds is generally 150,000 mPa51
Preferably lower than 10,000 mPa5 (measured at 80° C. using an Epprecht viscometer).

The structure of the phenol-terminated polyurethane or polyurea of formula I can be modified by process a), b) or #
-1C), but will vary depending on the functionality of the prepolymer group R1. In process a), this functionality can be controlled, for example, by the functionality of the hydroxyl-terminated, sulfhydryl-terminated or amine-terminated prepolymers, by the chain extenders that may be used, by the isocyanate for the preparation of compounds of the formula [a]. It will be determined by the functionality and by the ratio of the individual reactants. Among the compounds of formula I, those in which X represents 10- are preferred. Other preferred compounds of formula I are substantially free of isocyanate groups and contain at least two free phenolic hydroxyl groups, comprising a) al) optionally in combination with a chain extender. Also good,
a2) an adduct of a polyisocyanate to a prepolymer polyhydroxyl compound or a polysulfhydryl compound or to a mixture of such compounds; ) A compound which can be obtained by reacting at least one phenol having two or three phenolic hydroxyl groups with an amine phenol having one or two phenolic hydroxyl groups.

The compounds of formula I which are preferred in % are derived from prebolymer polyincyanates) a) having an average isocyanate functionality of 2 to 6.

Particular preference is given to compounds of the formula I in which component a1) is an adduct of a polyisocyanate to a hydroxyl-terminated brepolymer having an average molecular weight of from 150 to 10,000. Very particular preference is given to compounds of formula I in which the synthesis component used for the preparation of component al) is a hydroxyl-terminated polyether or polyester.

The synthetic components for the preparation of component a1) are preferably used in combination with chain extenders.

Very particular preference is given to compounds of formula I in which the polyisocyanates used for the preparation of component a1) are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates or triisocyanates.

In a preferred embodiment, the preparation of component a1) is carried out using hydroxyl-terminated polyethers or polyesters in the absence of chain extenders and with an excess of polyisocyanate or the like equivalent to the OH content. I,
And after reaction with polyphenol or aminephenol ■a, the following formula V: ■ (in the formula.

R3, m and n represent the above meanings.

r represents an integer between 1 and 3.

Y represents a group represented by 10--E or -NH-.

) t13 is r of the aliphatic, cycloaliphatic, aromatic or araliphatic polyisocyanate after removing the isocyanate group.
l represents a monovalent radical and represents a radical with the proviso that the index m and the radicals R3 and R13
may be different within the given molecule f'. ) is obtained.

This type of compound represented by formula (2) is preferred.

The index m is preferably 'EL<1. The index n is preferably 2
1 or 3. That's 9 times 2. The index r is preferably 1. Preferred compounds of formula V are those in which 1m is 1
, n represents 2 or 6, r represents 1,
Y represents a group represented by 10-, 13 is an aliphatic group,
R114 represents a group derived from an alicyclic or aromatic diisocyanate, and R114 is a hydroxyl-terminated polyether or polyether having a molecular weight of 150 to 10,000 after removal of the terminal hydroxyl group.
It is coated with a valent or trivalent group.

A very preferred compound represented by formula (1) is one in which 1m is 1
, n represents 6, r represents 1, Y represents a group represented by 10-, and R113
aliphatic -tfC represents a group derived from an alicyclic diisocyanate, and i'L14 represents a divalent or 6-valent polyalkylene ether-polyol having a molecular weight of 150 to 6000 after removal of the terminal hydroxyl group.
It represents a value group. Particularly preferred compounds of this last type are those of the above formula V in which n represents 2;
And R14 is the following formula■knee (C3H230zuTC8)128- (fund)
(During the ceremony.

S represents 3 or 4, X represents an integer from 5 to 40, and -C8H,5
-0- units are given fl, within the scope of the definition.

A given structural unit represented by 2 may differ within a given structural unit. ) represents the structural unit represented by.

An example of the structural unit represented by formula (■) is the following:
(CHI)-.

-(CH, -CH2-CH2-CH, -0) x-CH
2-CH2-C)12-CI-12- and copolymers containing these structural units.

Particularly preferred are compounds derived from bisphenols in which 1(, 3 in formula v are represented by formula (■)).

Other preferred polyurethanes or polyureas of the invention include a) substantially equivalent amounts of diisocyanate and less than 1% by weight of dihydroxyl-terminated or trihydroxyl-terminated polyethers or polyesters and hydroxyl-terminated grepolymers; b) with an amount of bisphenol or trisphenol substantially equivalent to the NGO content;

In another preferred embodiment, component a2) is prepared using amine-terminated polyalkylene ethers, in the absence of chain extenders, diisocyanate "tfc" equivalent to the NH2 content is added to their excess and l polyphenol or aminephenol lea
After the reaction with the following formula ■: (in the formula.

R3, m and n represent the above meanings, and Y represents a group represented by -0- or -NH-.

t represents 0 or 1.

R15 represents a divalent group of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanate after removing the isocyanate group, □ and RIM represents the amine group-terminated polyalkylene after removing the terminal NH, group. Represents the n-valent group of ether. ) is obtained.

Particularly preferable compounds represented by formula (1) are:

m represents 1, n represents 2 or 3, Y is 10-
represents a group covered with , and R15 is an aliphatic group.

A divalent or trivalent amine group-terminated polyalkylene ether which represents a group derived from an alicyclic or aromatic diisocyanate and has a molecular weight of 150 to 10,000 after the R+16 terminal amine group is removed. It represents the group of.

A very preferred compound represented by formula (1) is one in which 1m is 1
, n represents 2, t represents 0, Y represents -O
- represents a group.

Rlg represents a group derived from a divalent amine group-terminated polyalkylene ether having a molecular weight of 150 to 6,000.

A very preferred compound of the formula (3) is one in which 1m and t represent 1 and n represents 2.

R15 represents a divalent group of aliphatic or alicyclic diisocyanate after removing the isocyanate group, and
16 represents a group derived from a divalent amino group-terminated polyalkyl group having a molecular weight of 150 to 6,000.

Particularly preferred compounds of these last two types are those of the formula (1) wherein R16 is of the formula (2) or (2).

-f-C)iz-屓0-f-CHz) ke2 (to).

(In the formula, y is 5 to 90, preferably 10 to 70
, 2 represents 10 to 40, R17 represents an aliphatic diol group after removing two Ofi groups, and R1'' represents an aliphatic diol group after removing three OH groups. (represents a group of group triol).

Compounds of formula 1 can be used as curable mixtures with epoxide resins.

The curing action is provided by free phenolic hydroxyl groups. These curable mixtures can, of course, also contain other curing agents customary in epoxide resin technology.

-tfL The present invention therefore also relates to compositions containing 1) an epoxide compound having at least two 1,2-epoxide groups per molecule and 11) a compound of formula I above.

In principle, any compound customary in epoxide resin technology can be used as component 1). It is also possible to use mixtures of epoxide resins.

The following are examples of epoxide resins: ■) Compounds with at least two carboxyl groups in the molecule and shrimp chlorohydrin! 2 is polyglycidyl and poly-(β-methylglycidyl) ester which can be produced by reacting with β-methyl shrimp chlorohydrin. The reaction is advantageously carried out in the presence of a base.

Aliphatic polycarboxylic acids are compounds having at least two carboxyl groups in their molecules, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid. It is also possible.

Aromatic polycarboxylic acids such as phthalic acid and isophthalic acid 1fc can also be terephthalic acid.

■) A compound having at least two free alcoholic hydroxyl groups and/or phenolic hydroxyl groups and a suitably substituted shrimp chlorohydrin are combined under alkaline conditions, followed by an alkali treatment in the presence of an acid catalyst. Polyglycidyl reeds or poly-(β-methylglycidyl) ethers which can be produced by treatment and reaction.

Ethers of this type Fi1, such as acyclic alcohols, ethylene glycol, diethylene glycol and high molecular weight poly-(oxyethylene) glycols, furopane-1,2-diol and poly-(oxypropylene) glycol, globan-1 ,6-diol,
Butane-1+4-diol, poly-(oxytetramethylene) glycol, pentane-1,s-,-;ol, hexane-1,6-diol, hexane-2,4,6
-Triols, glycerol, 1.1.1-) Limethylol-derived from propane, pentaerythritol, sorbitol and polyevichlorohydrin.

However, they are, for example, alicyclic alcohols such as 1,6-dihydroxycyclohexane.

1.4-dihydroxycyclohexane, bis-(4-hydroxycyclohexyl)-methane.

It is also derived from 2,2-bis-(4-hydroxycyclohexyl)-propane or 1,1-bis-(hydroxymethyl)-cyclohex-6-dyne; N-bis-(2-hydroxyethyl)-aniline-f; +ttip.

Contains p'-bis-(2-hydroxyethylamino)-diphenylmethane.

The epoxide compound is derived from a mononuclear phenol, such as resorcinol or hydroquinone,
They are also polynuclear phenols such as bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis-( 4-hydroxyphenyl)-ethane, 2.2-bis-(4-hydroxyphenyl)-propane 17? : is 2,2-bis-(3I5
-dibromo-4-hydroxyphenyl)-cropanni,
and aldehydes such as formaldehyde, acetaldehyde, chloral or furturaldehyde with phenols such as phenol or 1 fc chlorine atoms in the nucleus.
is substituted with an alkyl group having 1 to 9 carbon atoms'
rL'fcphenol e.g. 4-chlorophenol, 2
They are also based on novolaks, which can be prepared by subjecting them to a condensation reaction with -methylphenol or 4-tertiary methylphenol or, as mentioned above, with bisphenols.

Glycidylated novolacs of oak nut oil are of particular interest for flexible compositions.

(2) Possible polyhydrochloride which can be prepared by dehydrochlorination of the reaction product of epichlorohydrin and an amine having at least two amine hydrogen atoms. j-(N-glycidyl) compound. Examples of these amines are aniline, n-butylamine, bis-
(4-aminophenyl)-methane, m-xylylenediamine or bis-(4-methylaminophenyl)-methane.

However, poly-(N-glycidyl) compounds are also triglycidyl isocyanurates.

Cycloalkylene urea e.g. ethylene urea or 1.3
- N,N'-diglycidyl derivatives of propylene urea and N,N'-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin.

■) poly-(S-glycidyl) compounds, dithiols derived from eg ethane-1,2-dithiol or pia-(4-mercatomethylphenyl) ether;
S-glycidyl derivative.

(2) Alicyclic epoxide resin 1 For example, bis-(6-epoxycyclobentyl) ether, 2,3-epoxycyclobentyl glycidyl ether.

1.2-His-(2,3-epoxycyclobentyloxy)-ethane or 447-nipoxycyclohexylmethyl sl, 4/-epoxycyclohexane carboxylate.

However, it is also possible to use epoxide resins in which the 1,2-epoxide group is attached to a foreign atom or functional group of the phosphorus, and these compounds can be used, for example, to 4-aminephenol, N, 0-triglycidyl Derivative, glycidyl ether of salicyl ether/glycidyl ether, N
-Glycidyl-N'-(2-glycidyloxyglopyl)-5,5-dimethylhydantoin or 2-glycidyloxy-1,6-bis-(5,5-dimethyl-1-glycidyl dantoiny-5-yl)- Contains propane.

Bisphenols, such as 2.2-bis-(4-hydroxyphenyl)-propane or bis-(4-hydroxyphenyl)-methane, novolaks formed by reaction of formaldehyde with phenol, especially the aliphatic diols mentioned above, butane- Polyglycidyl ethers of 1,4-diols and adducts of bisphenol A and glycidylated aliphatic diols are particularly preferred as epoxide resins.

The amounts of the epoxide compound 1) and the polyurethane or polyurea 11) of the composition according to the invention are such that the ratio of the hydroxyl equivalents of the polyurethane or polyurea 11) to the epoxide equivalents of the epoxide resin 1) is between 005 and 1.0;
Preferably, Q is selected to be between 1 and α8.

If a cured product with high impact resistance is desired, generally less than 50% by weight of component 11) is used based on the mixture of :) and 11). In this case 1-50
Preference is given to using % by weight, especially 5-25% by weight of component 11).

If a cured product with high flexibility is desired, it is of course also determined by the properties of the individual components 1) and 11).

Preferred flexible products have a glass transition temperature of the flexible phase of 0.
℃, preferably lower than 20℃.

Systems of this type can be homogeneous or heterogeneous.

The compositions containing all 1) and 11) may also be used in the form of fusible but still curable adducts.

The production of such fusible but still curable adducts can be achieved by combining an epoxide resin 1) and a phenol-terminated polyurethane or polyurea 11), if appropriate in the presence of a catalyst, known per se. Heat it using the method of
A melting process is performed, resulting in the formation of a fusible but still curable precondensate. Preference is given to using 20-50% by weight of component 11) relative to the amount of components 1) and i).

Examples of catalysts used are triphenylphosphine, tertiary amines, quaternary ammonium or phospho='7Am'E
7'C is chromium acetylacetonate.

The invention also relates to these adducts.

The curable mixture according to the invention may contain additional curing agents 11), which are of course known to those skilled in the art, such as aliphatic, cycloaliphatic, aromatic and heterocyclic amines, such as bis(4-amino phenyl)methane, aniline/formaldehyde resin, bis(4-aminophenyl)sulfone, propane-1,3-diamine, hexamethylenediamine,
Diethylenetriamine, triethylenetetraamine, 2
,2.4-)dimethylhexane-1,6-diamine, m
-xylylene-diamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane and 3-aminomethyl-3,5,5-)
Listylcyclohexylamine (inholone-diamine); polyaminoamides, such as those prepared from aliphatic polyamines and trimerized I or trimerized fatty acids; polyphenols, such as resorcinol, hydroquinone% 2.
2-bis(4-hydroxyphenyl)propane (bisphenol A and phenol/aldehyde resins; polythiols, e.g. Thiokols J
Polythiols commercially available under the names of polycarboxylic acids and their anhydrides 1, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride.

Hexachloroendomethylenetetrahydrophthalic anhydride, pyromellitic anhydride, benzophenone-3,A
/ 4.4. /-tetracarboxylic dianhydride, the acid of the above-mentioned anhydride, and isophthalic acid and terephthalic acid. Curing agents with catalytic action, such as tertiary amines [e.g. 2.4.6-)! J-susu-dimethylaminoethyl)
-phenol]; imidazole 1fc, Mannich base; alkali metal alcoholate (e.g. Na alcoholate of 2,4-hydroxy-3-hydroxymethylpentane); tin salt of alkanoic acid (e.g. tin octanoate), Friedel- Craft Catalysts 1 Complexes and chelates of +:rt etc. obtained by reaction of boron trifluoride and boron trichloride, and boron trifluoride with e.g. Can also be used.In addition to these, 1v curing accelerator
) can also be used.

Examples of curing accelerators iv) are tertiary amines, their salts or quaternary ammonium compounds, such as bendimethylamine,
2.4.6-) Lis-(dimethylaminomethyl)-phenol, 1-methylimidazole, 2-ethyl-4-
Methylimidazole, 4-aminopyridine, tribentylammonium ferulate or tetramethylammonium chloride: or alkali metal alcoholates, such as Na alcoholate of 2,4-dihydroxy-3-hydroxymethylpentane; or substituted ureas; e.g. N
-(4-chlorophenyl)-N',N'-dimethylurea Primary is N-(6-chloro-4-methylphenyl) -
N/, N/-dimethylurea (chlortoluron).

Preference is given to thermosetting systems consisting of components I) and 11) in combination with primary and/or secondary aromatic amines or amidines as hardeners 1iI).

The amount of curing agent iii) i or accelerator iv) depends on the type of curing agent and will be selected by the person skilled in the art in a manner known per se. A preferred curing agent is dicyandiamide. In this case, it is preferable to use 0.7-ns mole of curing agent per mole of epoxide group.

Depending on the curing agent, curing can be carried out at fairly low temperatures or at fairly high temperatures. Generally, the curing temperature for thermal curing is between 80 and 250°C, preferably between 100 and 180°C.

If desired, the curing may be carried out in two stages, for example by interrupting the curing process or, if a fairly high temperature curing agent is used, by curing the curable mixture at a fairly low temperature to some extent I. . The product thus obtained is.

It is a precondensate that is still fusible and soluble (so-called "B-stage resin") and is suitable, for example, for compression molding materials, sintered powders or brevregs.

If desired, active diluents 1 such as styrene oxide, butyl glycidyl ether.

2,2.4-) Limethylphenylglycidyl ether, phenylglycidyl ether, cresylglycidyl ether or synthetic highly branched glycidyl esters of predominantly tertiary aliphatic monocarboxylic acids to reduce the viscosity. It may also be added to the curable mixture. Other customary additives that the mixture according to the invention may contain are plasticizers.

Bulking agents, fillers and reinforcing agents such as coal tar, bitimen, textile fibers, glass fibers.

Asbestos fibers, boron fibers, carbon fibers, inorganic silicates, mica, silica sand, aluminum oxide hydrate, bentonite, kaolin, wollastonite, silicate airgel I or metal powder 1, such as aluminum powder, or iron powder, and Pigments and dyes 1 For example carbon black, oxide colors (o
xidecolor) and titanium dioxide, flame retardants,
Thixotropic agents, flow control agents 1 such as silicones, waxes and nutheate, some of which were also used as mold release agents. It is an adhesion promoter, antioxidant and light stabilizer.

The mixtures according to the invention can be used for example as adhesive bonding films, matrix resins, lacquers, sealing compositions.
mposition) i or as a batt or very generally for the production of cured products. -f
1, eg paint, in unfilled reed or filled form, with formulations adapted in each case to the particular field of use.

Coating compositions, lunkers, compression molding materials, V performance resins, casting resins, impregnation resins, lamination resins.

Can be used as base resin and adhesive.

The invention also relates to the use of the mixtures according to the invention for the above-mentioned purposes and to cured products.

[Examples and effects of the invention]

The following examples illustrate the invention.

Preparation of Compound A Example 1 Methylene diphenyl diisocyanate 1002 was first placed in a dry Fujinoko with a ground joint under nitrogen atmosphere and heated to 100°C.
and polypropylene glycol (Mw=2000
) 3547% and) Lime f r:x -propane 1.81 and dibutyltin dilaurate 0.1 d'i8
was added over 15 minutes at 0°C and the mixture was heated to 80°C.
Stir for 2 hours. 100°C and 1', s s P
Tahe 6'-diallyl bisphenol A was dried at a pressure.
135S' is then added and the mixture is stirred at 80° C. for 2 hours and 120° C. for 45 minutes at 1, when free isocyanate can no longer be detected. This gives a viscous resin with the following analytical data.

Viscosity: η8゜=112600 mPas Phenol content: 27 phenol content (GPC): Mn-=2350. Mw/
Mn=a 6 Example 2 Anhydrous polypropylene glycol (Mw = 2000
) 354p,) 1.81 of rimethylolpropane and 0.1aJ of dibutyltin dilaurate to 54.4f of hexamethylene diisocyanate? at 100° C. and under a nitrogen atmosphere. The mixture was stirred at 1100°C for 2 hours,
And after the mencyanate content has decreased to below 4%,
This blend polymer was poured into anhydrous 3,3'-diallylbisphenol A1651 at a total temperature of 8 Ω°C and the mixture was stirred at 80°C at 1° C. until free isocyanate could no longer be detected.
Stir for 2.5 hours at 100°C and 30 minutes at 100°C. This gives a viscous resin with the following analytical data.

Viscosity: 774o=128600mPa5 Phenol content: 2.5 Portion/K-q Molecular weight (GPC): Mn=1
260. Mw/Mn=11.4 Example 3 Hexamethylene diisocyanate 84f.

The ground joint was first placed in a dry flask with 6,000 strands under a nitrogen atmosphere, and 500 t of anhydrous polyglobylene glycol (Mw = 2000) was added over 1 hour at 85°C and allowed to cool. The mixture is stirred at 100°C for 2 hours and at 135°C for 1 hour to reach an isocyanate content of 52%. This prepolymer is 3,6
0.1 ml of the mixture is added at 100<0>C. After stirring for 6 hours at 100 DEG C., free isocyanate can no longer be detected, and this gives 500 V of a viscous resin with the following analytical data.

Viscosity: 14 (,=590000 mPa5 Phenol content: 1.4 equivalent/Kg Molecular weight (()PC): Mn=2285. Mw/Mn
=24 Example 4 Hexamethylene diisocyanate 67.25'.

Anhydrous polypropylene glycol (M
w=2000) 354P, trimethylolpropane 1.
81i' and dibutyltin dilaurate a 1 ttt
l f Added over 15 minutes at 85°C.

and stir the mixture at 100° C. for 2 hours.

This prepolymer is added to anhydrous 3,6'-diallylbisphenol A135f at 100°C and the mixture is stirred at 100°C for 5 hours and at 160°C for 2 hours.

This gives a viscous resin with the following analytical data.

Viscosity: '7to = +133000mPa5molecular weight (
, GPC): Mn=, 1420. Mw/Mn=11
．． 5 phenol content: 1,6 equivalents/Ni Example 5 hexamethylene diisocyanate) 40.1"i.

first placed under a nitrogen atmosphere into a dry flask with ground joints and anhydrous polybutylene glycol (MW
=2000)265.57. ) Ri J f.

- Lubroban 1.35f and dibutyltin dilaure)
0. J rd is added at 100°C and the mixture is stirred at 100°C for 2 hours. The produced prepolymer was converted into anhydrous 3,3'-diallylbisphenol A101.3.
ji' at 80°C, the mixture was heated to 100°C at -tl, at which free isocyanate could no longer be detected.
Stir for 4 hours at 110°C and 6 hours at 110°C. This gives a viscous resin with the following analytical data.

Viscosity: ηgo -56000rrrP a s Molecular weight (
GPC): Mn-=1250. Mw/Mn=17 Phenol content: 1.55 equivalents/nori Example 6 Hexamethylene diisocyanate) 54.47i.

Anhydrous polypropylene glycol (Mw=
2DOO) 3544F, )'Jnor+o-rupropane 1
．． 81 and dibutyltin dilaurate 01 were added continuously at 100°C and at 1 to reach an isocyanate content of 55%.

Mixture i Stir at 100°C for 2 hours. This prepolymer is added to a solution of bisphenol A101' in 5f30tttl of anhydrous dioxane and the mixture is boiled under reflux for 5 hours. dioxane then 100℃71.33
A viscous resin is obtained which has the following analytical data.

Viscosity 2 η8o-60160 mPaS Molecular weight (GPC): Mw = 31500 Phenol content: 1.8 equivalents/edge (/9) Example 7 Hexamethylene diisocyanate 544F was initially placed in a dry flask with a seam joint under a nitrogen atmosphere. and anhydrous polypropylene glycol: 7-l (My=200
0) 354y,) Limeterolpropane 1.8F and dibutyltin dilaurate [Ll- are added continuously at 100°C and the mixture is stirred for 2 hours at 100°C until an isocyanate content of 2.5% is reached. . This prepolymer is added under reduced pressure to a solution of bisphenol A 100y in anhydrous dioxane 300d and the mixture is boiled under reflux for 5 hours. Dioxane was then heated at 100℃/
A viscous resin is obtained which is removed at 1.53 Pa and has the following analytical data.

Viscosity two η function = 9216 ompa8 Molecular weight (GPC): Mw = 25260, Mn = 84
0.

Mw/Mn = 50 Phenol content = 1.8 eq/Example 8 54.47% of hexamethylene diisocyanate was first placed under a nitrogen atmosphere in a dry flask with a dowel joint and anhydrous polypropylene glycol (Mw =
2ooo)ss4y,)limethylolpropane 1.8F
and dibutyltin dilaure) (Lld continuously at 10
It is added at 0°C and the mixture is stirred at 100°C for 2 hours. This prepolymer was mixed with anhydrous dioxane at 300 mA.
! and the mixture is boiled under reflux for 5 hours.

After the dioxane is then removed at 90° C./1.33 Pa a viscous resin is obtained with the following analytical data.

Viscosity: j7sonia 1700mPa5 molecular weight (GP
C): Mw=23720, Mn=560.

Mw/Mn = 42 Phenol content: 1.7 weight/Kt Example 9 54.4 F of hexamethelene diacyanate was first placed under a nitrogen atmosphere in a dry flask with a ground joint, and anhydrous polypropylene glycol ( MW=200
0) 354P1) Limeterolpropane 1.8y and diptyltin dilaure) [Lld continuously at 100°C
and the mixture is stirred at 100° C. for 2 hours. The prepolymer produced is added to a solution of 45'-diallylbisphenol A135y in 300d of anhydrous toluene and the mixture is boiled under reflux for 6 hours. The toluene is then removed at 110° C./133 Pa to obtain a viscous resin with the following analytical data.

Viscosity: , 774G = 116500 mPa5 molecules it (GPC): Mw = 147s o , Mn = =
944.

Mw/Mn=16 Phenol content=1.6 equivalents/Kf Example 10 Inphorone diisocyanate 76y was initially placed in a dry flask with ground joints under nitrogen atmosphere,
and polybutylene glycol (Mw=2000)
305y, trimethylolpropane 1.5F and dibutyltin dilaurate 0,1*J continuously at 100℃
and the mixture is stirred at 100° C. for 2 hours until an isocyanate content of 5.3% is reached. This prepolymer'l [1i water 3.3'-diallylbisphenol A115F solution was added and the mixture was stirred at 80°C for 30 minutes until free isocyanate could no longer be detected.
Stir for 30 minutes at 105°C. This gives a viscous resin with the following analytical data.

Viscosity: ηso: 64000 mPa5 molecular weight (GPC
): Mn=1740. Mw/Mn=&8 Phenol content: 1.56 equivalents/Kt Example 11 Isophorone diisocyanate aasy was first placed in a dry flask with ground joints under nitrogen atmosphere and polypropylene glycol (Mw=2000)
354F,) 1.82 - rimeterol propane and 0.1 - dibutyltin dilaurate were added continuously at 100 °C for 15
It is added over a period of minutes and the mixture is stirred at 100° C. for 2 hours until an isocyanate content of 4.0% is reached.

This prepolymer was added to an anhydrous 3'-diallylbisphenol A135 solution and the mixture was stirred at 80°C for 3 hours until free isocyanate could no longer be detected.
Stir for 30 minutes at 100°C. This gives a viscous resin with the following analytical data.

Viscosity: t) @6 = 12640 mPa5 molecular weight (GP
C): Mn=t630. Mw/Mn=7.2 Phenol content: 1.5 equivalents/Kf Example 12 Isophorone diisocyanate 8a8y was initially placed in a dry flask with ground joints under nitrogen atmosphere,
and polypropylene glycol (MW=3000)
3549. ) Rimeterolpropane 1.8y and dibutyltin dilaurate α1d were added continuously at 100°C for 15
It is added over a period of minutes and the mixture is stirred at 100° C. for 2 hours until an isocyanate content of 4.0% is reached. p-Aminephenol 44y is then added and the mixture is stirred at 120° C. for 3 hours. This gives a viscous resin with the following analytical data.

Viscosity: η=a2800mPag Molecular weight (GPC): Mn=1090. Mw/Mn=5.
87 x/-k content: a83/11/Kt Example 1
3 Isophorone diisocyanate 8a8j+ is first placed in a dry flask with ground joints under nitrogen atmosphere and polypropylene glycol (Mw=2000
) 354y,) 1.8y of limethylolpropane and 11mg of dibutyltin dilaurate were added continuously at 100°C.
It is added over 5 minutes and the mixture is stirred at 100° C. for 2 hours until an isocyanate content of 4.0 is reached.

118 ml of bisphenol A is then added and the mixture is stirred at 120° C. for 3 hours until free isocyanate can no longer be detected. This gives a viscous resin with the following analytical data.

Viscosity 2 ηBo = 11560 mPa5 Molecular weight (GPC): Mn = 620. Mw/Mn=9.3
Phenol content = 2-4 equivalents/noodles Example 14 Mixture of toluylene diisocyanate isomers 701,
First placed under a nitrogen atmosphere into a dry flask with mating joints and filled with polypropylene glycol (Mw
=2000)354p.

1.8 y of trimethylolpropane and 0.1 d of diptyltin dilaurate are added continuously at 100° C. and the mixture is stirred at 100° C. for 2 hours until an isocyanate content of 4.0% is reached.

This prepolymer is diallylbisphenol A135y
and the mixture is stirred at 100° C. for 3 hours until free isocyanate can no longer be detected. This yields a viscous resin that meets the analytical data below.

Viscosity: η80=17920mPa5 Molecular weight (GPC): Mn=2000. Mw/Mn-&4
Phenol content: 2.2 equivalents/Kt Example 15 Bisphenol A diglycidyl ether (epoxide content 5.4 equivalents fM/h) zooy and 7 from Example 2
The di-nol-containing urethane prepolymer 200y is stirred in the presence of triphenylphosphine 4y at 140° C. for 2 hours under a nitrogen atmosphere.

This gives a viscous resin with the following analytical data.

Epoxide content: 1.8 equivalent M/hc theoretical value 1.4 equivalent/
lk) Viscosity = ηg = 17280 mPag Example 16 Hexamethylene diylene cyanide) 54.45E is first placed under a perforated atmosphere in a dry flask with a mating joint, and anhydrous dihydroxyl-terminated polypropylene glycol ( Mw=2000) 200y and dibutyltin dilaurate α1Ke are added at 100° C. over 60 minutes.

1.4-Cyclohexane dimetatool 11. OjF was then added to this reaction mixture, stirring was carried out at 100°C for 60 minutes, and the prepolymer thus obtained was added to 3'-diallylbisphenol A135y at 100°C under nitrogen atmosphere over 30 minutes. do. 3 at 100℃
After stirring for an hour, free isocyanate can no longer be detected,
A viscous resin having the following analytical data is obtained.

Viscosity: 17go=9600 mPa5 Example 1 Finphorone diisocyanate 519f and dibutyltin dilaurate Q, 1d were first placed in a dry flask with a mating joint under a nitrogen atmosphere and anhydrous dihydroxyl group-terminated polypropylene glycol: l- (M-ff
=2000) 137F, and trihydroxyl group-terminated polypropylene glycerol:7-l (Mtr==4ooo)6
Add asyo mixture over 1 hour at 100°C. After stirring the mixture at 100 DEG C. for 2 hours, the prepolymer is added to the 43'-diallylbisphenol A5ay and the mixture is stirred for 3 hours until free isocyanate can no longer be detected. This gives a viscous resin with the following analytical data.

Viscosity: ηo: 246000 mPa5 Phenol content: 1.15 equivalent/molecular weight (GPC): Mn=1830. Mw/Mn=16
Example 18 Inphorone diisocyanate 71.8jE is initially placed under a nitrogen atmosphere in a dry flask with a -1-b mating joint and anhydrous dihydroxyl-terminated polytetrahydro7rane (Mv=zooO) 3say.

A mixture of 1.8y trimethylolpropane and dibutyltin dilaurate algo is added and the mixture is stirred at 100°C for 2 hours until an isocyanate content of 2-3% is reached. The prepolymer thus obtained was dissolved in 45'-diallylbisphenol Al34P at 8
Pour at 0℃.

After stirring for 3 hours at 80° C., free isocyanate can no longer be detected and a viscous resin is obtained with the following analytical data.

Viscosity: η = 37760 mPa5, Molecular weight (GPC): Mn = 1520. Mw/Mn=
1 51 Example 19 Inphorone diisocyanate 8a8y was first placed under a nitrogen atmosphere in a dry flask with ground joints and anhydrous dihydroxyl-terminated polycaprolactone (M, = 2 o o o ) 554y, trimethylol Propane t8 and diptyltin dilaurate α1-
Add the mixture at 80° C. over 30 minutes with stirring. After 2 hours, the prepolymer thus obtained is added to 43% diallylbisphenol A150y, and the mixture is stirred for a further 3 hours until free isocyanate can no longer be detected. This gives a semi-solid resin with the following analytical data.

Viscosity: η5o=5760 mPa5 Example 20 Inphoron diisocyanate 9a4 was first placed in a dry flask with a ground joint under a nitrogen atmosphere,
Then, 1.8F of trimethylolpropane and dibutyltin dilaurate α1d are added at 80°C. A mixture of dihydroxyl-terminated polypropylene glycol and bis-(aminopropyl)-polytetrahydrofuran (Mn=750) was poured over a period of 2 hours,
This mixture was allowed to react for 2 hours and finally 3.3′-
Add diallylbisphenol Al50y. After reacting this mixture at 80° C. for 3 hours, free isocyanate can no longer be detected and a viscous resin is obtained with the following analytical data.

Viscosity: 17 questions = 40960mPa5 Molecular weight (GPC): Mn = 12oO, My/Mn = 1g
Example 21 To phosgenate bis-(isocyanatopropyl)-polytetrahydrofuran (molecular weight 750 and isocyanate content &5% neutralized with anhydrous HCI) in a dry flask with mating joints. 11.63F of p-aminophenol is added to 40y under a nitrogen atmosphere. 80℃
After stirring for 3 hours at , a waxy resin is obtained with the following analytical data.

Viscosity: 15=399400 mPa5 Phenol content: 247 equivalents/Kr Example 22 A mixture of 3'-diallyl bisphenol A24.6F and dibutyltin dilaurate α1- in a dry flask with a seam joint was heated with bis-( isocyanatopropyl)-polytetrahydrofuran (anhydrous H
A molecule 1750 neutralized with C7 and an isocyanate content of 30y (prepared by phosgenation of bisaminopropyl-tetrahydrofuran of 50%) is added.

After stirring for 3 hours at 100° C., a viscous resin is obtained with the following analytical data.

Viscosity: 77, = 122880 mPa5 Phenol content: 2.88 eq/Example 23 Bis-(isocyanyl) is added to a mixture of 3'-diallyl bisphenol A2&OP and dibutyltin dilaurate α11E/ in a dry flask with ground joints under a nitrogen atmosphere. 50 y of bis-aminopropyl-polytetrahydrofuran (manufactured by Toyosi after phosgenation of bis-aminopropyl-polytetrahydrofuran with a molecular weight of 1100 and an isocyanate content of A1%, neutralized with dry HCJ) are added. After stirring for 5 hours at 80° C., a viscous resin is obtained with the following analytical data.

Viscosity: 1B = 21600 mPa5 Phenol content 22.18 parts/Kf Example 24 Bis-(isocyanatopropyl)-polytetrahydrofuran (molecular weight 1 neutralized with anhydrous HCl) in a dry flask
To 50y (prepared by phosgenation of bisaminopropyl-polytetrahydrofuran with an isocyanate content of 51% and an isocyanate content of 51%) is added 10y of p-aminephenol under a nitrogen atmosphere, and the mixture is stirred at 100°C for 5 hours. This gives a viscous resin with the following analytical data.

Viscosity: 1B = 67840 mPa5 Phenol content: 2.03 equivalents/Kf Example 25 Bis-(isocyanatopropyl)-polytetrahydrofuran (neutralized with anhydrous HCI, molecular weight 2) in a dry flask
100 and bisaminopropyl-polytetrahydrofuran with an isocyanate content of 1.2%) 50y is added with p-aminephenol 5.1F under a nitrogen atmosphere. Stirring at 100° C. for 4 hours gives a viscous resin with the following analytical data.

Viscosity: η25 = 25600 mPa5 Phenol content I#: 1.61 equivalent/Kf Example 26 He3'-diallyl bisphenol AI in dry flask
A mixture of 4.6F and dibutyltin dilaurate Q, 1at was treated with bis-(incyanatopropyl)- under a nitrogen atmosphere.
polytetrahydro7rane (molecule 1 neutralized with anhydrous HC1)
2100 and 50y (prepared by phosgenation of bisaminopropyl-polytetrahydrofuran with an isocyanate content of 1.2%) are added. After stirring for 4 hours at 100° C., a viscous resin is obtained with the following analytical data.

Viscosity: η25 = 2 < 320 mPa5 Phenol content 1 = 11.75 equivalents/(Example 27 Diisocyanate group-terminated polypropylene glycol in dry flask [by Texaco, !7
Manufactured Jeffamine 0D
Prepared by phosgenation of 230, isocyanate content 2
0ch] 201 under a nitrogen atmosphere, 43'-diallylbisphenol A5L5f and diptyltin dilaure I/α
Add 1 ml of the mixture.

Heating at 100° C. for 4 hours yields a wax resin with the following analytical data.

Viscosity = ηB6 = 1520 mPa5 Phenol content = 476 equivalents/Kf Example 28 Diisocyanate group-terminated polypropylene glycol (bisamino group-terminated polypropylene glycol with a molecular weight of 230, available as Shefamine D230 manufactured by Texaco, was phosgenated. P-amine phenol 215f is added to 25F (prepared with isocyanate content 20%) under a nitrogen atmosphere. After stirring for 3 hours at 100° C., a viscous resin is obtained with the following analytical data.

Viscosity: ηlm = 2800 mPaa mPa Mitsuenol, 2 equivalents/noodles Example 29 He3'-diallyl bisphenol A1 in dry flask
a81 and diptyltin dilaurate [Lld] under a nitrogen atmosphere and neutralized with diisocyanate-terminated polypropylene glycol (available from Texaco as Shefamine D2000 and anhydrous HC).
Prepared by phosgenation of 000 bis-amino group terminated polypropylene glycol, isocyanate content 56%) 29.27% is added. After stirring for 6 hours at 100° C., a viscous resin without isocyanate groups is obtained having the following analytical data.

Viscosity: V,:4 a 160 mPa5 Phenol content: 1.73 eq./noodles Example 30 Diisocyanate-terminated polypropylene glycol (Chefamine) in dry flask available from Texaco as 2000 and neutralized with anhydrous HCJ p-aminophenol tqy is added to AjL6y under a nitrogen atmosphere, prepared by phosgenating bis-amino group-terminated polypropylene glycol having a molecular weight of 2000, and having an isocyanate content of 56. Stirring at 100° C. for 5 hours gives a strong viscous resin with isocyanate groups having the following analytical data.

Viscosity: 2η, 5 = 63360 mPa5 Phenol content: α96 equivalents/Example 31 A mixture of 105 m/3.3'-diallylbisphenol A (7.2 Amine 1) is commercially available as 4000 and has a molecular weight of 4000 neutralized with anhydrous H (J).
prepared by phosgenating bis-amino group-terminated polypropylene glycol, isocyanate content t8%)
Add 40F. Heating at 100° C. for 6 hours gives a viscous resin free of isocyanate groups with the following analytical data.

Viscosity = ηB = 20480 mPa5 Phenol content: α97 equivalents/Noodles Example '52 Bis-amino group terminated polypropylene of molecular weight 4000, commercially available as diisocyanate-terminated polypropylene glycol (Chefamine 1) 4000 and neutralized with anhydrous HCI. By adding p-amine phenol 3F to 50f (prepared by phosgenation of glycol, isocyanate content t8%) under a nitrogen atmosphere, a viscous resin without isocyanate groups having the following analytical data is obtained. Stir at ℃ for 6 hours.

Viscosity 2 η2s=704 QmPas mPa-Al content: α52 equivalent/(Example 53 Triisocyanate group-terminated polypropylene glycol (
Commercially available as Shefamine T405 and prepared by phosgenation of polypropylene glycol triamine of molecular weight 400, neutralized with anhydrous HC, isocyanate content 1 & 1%) at 50 F under nitrogen atmosphere, p- Amine phenol 415y is added and the mixture is treated at 100° C. for 3 hours and at 140° C. for 2 hours. This gives a viscous resin without isocyanate groups having the following analytical data.

Viscosity: '7u=24960mPa5 Phenol content: α84 equivalent/Example 54 Triisocyanate group-terminated polypropylene glycol (
A small amount was prepared by phosgenating polypropylene glycol triamine with a molecular weight of 3000, commercially available as Chefamine']'1000, and p-aminephenol 55F was added to the isocyanate content (t6%) 50% under a nitrogen atmosphere, This mixture is boiled at 100° C. for 5 hours. This gives a viscous resin with the following analytical data.

Viscosity: 1B=89600 mPa5 Phenol content: 1.0 equivalent/Example 35 Triisocyanate group-terminated polypropylene glycol (
Prepared by phosgenation of polypropylene glycol triamine of molecular weight 5000, commercially available as Chefamine '1'5ooo and neutralized with anhydrous HCJ, containing 1.5% isocyanate) under a nitrogen atmosphere. Bottom, add p-aminophenol & 27y,
This mixture is stirred at 100° C. for 3 hours. With this K, a viscous resin having no isocyanate groups and having the following analytical data is obtained.

Viscosity: η, 5=58880 mPa5 7x/Content: CL55 equivalent/Kt Example 36 Triisocyanate group-terminated polypropylene glycol (
Prepared by phosgenation of polypropylene glycol triamine of molecular weight 3000, available commercially as Chefamine T3000 and neutralized with anhydrous HC, isocyanate content 1.6% under nitrogen atmosphere. 43'-diallylbisphenol A15.4y
and diptyltin dilaure) n1 m/ and the mixture was stirred at 100 °C for 6 hrs until a resin without isocyanate groups was obtained with the following analytical data.
time and heat at 140° C. for 2 hours.

Viscosity = ηH = 87040 mPa5 Phenol content: 1.53 equivalent/Noodle Example 37 He3'-diallyl bisphenol A991, molecular weight 40
00 diamino-terminated polypropylene glycol (di
A mixture of 77mmyp4000)400F and dibutyltindilaure)Out/ is added to hexamethylene diisocyanate 5α4y over a period of 20 minutes under a nitrogen atmosphere. This mixture is then stirred at 110° C. for 5 hours. This gives a viscous resin without isocyanate groups having the following analytical data.

Viscosity: η, = 1q 4 b o 0 mPa5 molecular weight (
GPC): Mn=2900. Mw/Mn=5.7 Phenol content: 1.14 equivalent/l Example 68 Diamino group-terminated polypropylene glycol (Chefamine D4000) 400f, molecular weight 50
00 triamino group-terminated polypropylene glycol (Chefamine T 5000) 50foxhis,s'-
A mixture of diallyl bisphenol A 341 is added to inphorone diisocyanate 511 over a period of 30 minutes under a nitrogen atmosphere. After stirring for 4 hours at 110° C., a viscous resin without isocyanate groups is obtained with the following analytical data.

Viscosity: ηa (, = 15 + S160m pas molecular weight (G
PC): Mn=3ooo, M%v/Mr1-56 Phenol content: α93 equivalents/example 39 Diamino-terminated polyglopylene glycol (Chefamine D, aooo) with a molecular weight of 4000 4oor.

A mixture of 230 molecular weight diamino-terminated polypropylene glycol (Chefamine D230) 23r and 3.3'-Schiff 1J rubisphenol A166t is added to Inphoron diisocyanate 892 over 60 minutes under a nitrogen atmosphere. This mixture' is then stirred at 100° C. for 1 hour, 0.1 m/i of dibutyltin dilauret) is added and the mixture is stirred at 100° C. for 6 hours. This yields a resin free of isocyanate groups and having the following properties.

Viscosity: ηao = 97280 m pas molecular weight (G
P C): Mn = 2400, M”4n =
5.3 Phenol content: 165 equivalents/kf Example 40 Diamino-terminated polyglopylene glycol with a molecular weight of 2000 (Chefamine D2000) 400f and 3,
A mixture of 3'-diallylbisphenol A 136f is added to Inphorondiincyane 89f over 60 minutes without heating. Diptyltin dilaure) 0.
1d'z is then added and the mixture is boiled at 100° C. for 3 hours. This gives a resin without isocyanate groups having the following analytical data.

Viscosity: η1. . = 7040 m pas molecular weight (GP
C): Mn-2400, MvMrl-6,9 phenol content = 168 equivalents/kg 1 m (0-phenylene carbonate) 27.2 ri under nitrogen atmosphere, bisaminopropyl-polybutylene carbonate:! −
Le (Mn = 11 DO) 10! Reaction with M' in the presence of dibutyltin oxide 052 at 120° C. for 6 hours yields a viscous resin with the following analytical data.

Viscosity (emprecht): 71680 mpas (25°C
) Phenol content: 1.76 equivalents/m2 Example 42 Gubenzoxacilone 271 was mixed with bisaminobrobyl-polybutyreciglyco-k (Mn=
1100) 1055' in the presence of 0.5y of dibutyltin oxide at 160°C for 6 hours, a viscous resin is obtained with the following analytical data.

Viscosity (Emprecht): 87040 mpas (25
°C) Phenol content: 187 equivalents/kg Example 43 Styrene/acrylonitrile [union carbide (u
hydroxyl-terminated polyalkylene ether 3162 grafted with Niax 24-32] produced by Nion Carbide;
A mixture of diptyltin dilaurate 01 and trimethylolpropane 0.99 is added to xamethylene diisocyanate 2z21 at 100 DEG C. over a period of 1 hour under a nitrogen atmosphere. After a further 2 hours, this isocyanate group-terminated prepolymer was converted into diallylbisphenol A68. of and the mixture is stirred for 3 hours at 2ioo° C. until free isocyanate can no longer be detected. This gives a phenol-terminated graft polymer with the following analytical data.

Viscosity (Emprecht'I: 40900 mpas (
80°C) Example 44 Acrylonitrile 125g, styrene 3Z5? and azoisobutyronitrile 052 in a nitrogen atmosphere F
It is added to 354 g of dihydroxyl-terminated polypropylene L/7 (Mw=2000) at 75°C over 2 hours, and the mixture is allowed to react at an initial temperature of 80-85°C for 4 hours. After adding diptyltin dilaurate 01-, the graft polymer is poured into hexamethylene diisocyanate 54.45F over 1 hour. 1
After stirring for 6 hours at 00 DEG C., the isocyanate-terminated graft polymer thus obtained is added to o,o'-diallylbisphenol A135r and the mixture is reacted at 100 DEG C. for 2 hours. This gives a resin with the following analytical data.

Viscosity (Emprecht): 158,720 mpas (40
°C) Phenol content: 17 equivalents/kf Example 45 Styrene 501 and azoin butyronitrile 05 g'
Example 4 except that a mixture of
Repeat operation 4 and obtain a phenolic-containing resin having the following analytical data.

Viscosity (Emprecht): 143360 mpas (40
℃) Phenol content = 16 equivalents/kr Example 46 Isophorone diisocyanate 881 was added to 11. ')”・
First placed under a nitrogen atmosphere into a dry flask with an odor of gold, and containing a mixture of 25 hydroxyl endpoints (AH, Co RD 45HT) and 0.1 td of dibutyltin dilaurate. Add over 1 hour at 100° C. with stirring.

After stirring for 1 hour, anhydrous dihydroxyl group-terminated polybutylene glycol (Mn=2000) 5005F
was added over a period of 1 hour, and the mixture was then heated to 100
Stir at ℃ for 2 hours. The isocyanate group-terminated prepolymer obtained in this way was removed from water and then heated to 3.3'
- Diallyl bisphenol A is added to 150 liters. 10
After stirring for 6 hours at 0° C., a viscous resin without isocyanate groups is obtained with the following analytical data.

Viscosity (emprecht): ηg. =56520 m pa
s Phenol content: 168 equivalents/Molecular weight (GPC): Mn=1700. MW/Mn=90
Example”-7 Hydroxyl group-terminated polybutadiene (ARCOfLD4
5HT) 50f and polybutylene glycol 2502
The prepolymer was produced in the same manner as in Example 46, except that .

This gives a viscous resin without isocyanate groups having the following analytical data.

Viscosity (emprecht) η86 = 84480 mpas
Phenol content: 1.76 equivalent/Ume molecular weight (GPC): Mn=1890, Mw/Mn
= 9.1B, Usage Example Bisphenol A diglycidyl ether (epoxide content: 54 equivalents/kf) 50f, Diandiamide 3.8
Chlortoruron 161, pyrogenic silica (Aerosil 380) 0.5f and chalk (Darcal 5) 2O
r is mixed with compound 601 obtained according to Example 1 in a six roll mill.

An adhesive layer was manufactured with the following results.

Lap shear strength on degreased steel: 22.2 N/mrn2 Glass transition temperature 286°C [Dupont 90
T-peel strength on degreased steel: 3.6 N7m (100%
Cohesive failure) Bisphenol A diglycidyl ether (epoxide content: 54 equivalents/ky) soy, dicyandiamide 6.8
? , Chlortoruron 1. Filter 2, pyrogenic silica (Aerosil 380) 0.57 and chalk (Darcal 5)
200 r is mixed with compound 30 iF obtained according to Example 2 in a six roll mill. The adhesive layer is manufactured,
The following results were obtained.

Lap shear strength on degreased steel: 28 N/ied glass transition temperature near 0°C (measured by dynamic mechanical spectroscopy on a DuPont 90-mouth calorimeter) 0.8 m thick degreased steel Top T-type peel strength: 49 N/cod (90-100% cohesive failure) Example ■ Epoxy cashew oil novolac with epoxide content of 22 equivalents/kg (cashew oil is reacted with formaldehyde, then shrimp chlorohydrin (prepared by glycidylation with) 151 and the phenolic urethane polymer 157 from Example 2 as well as bisphenolic diglyphyl ether 107, diluent (Actrell 400) 3r, wollastonite P18f, talc 41,
A mixture of pyrogenic silica (Aerosol 380) 06R, 2-cyandiamide 102 and Chlortoruronite was cured (60 minutes at 180°C) to 2.9 N on a degreased and sandblasted 15mm thick aluminum plate.
A flexible composition is obtained with a lap shear strength of /m2 and a T-peel strength of 1.4 N/11111 on degreased 38 mm thick steel plate.

Claims (25)

[Claims] (1) The following formula I: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, m represents 1 or 2, n represents 2 or 6, and R^1 is soluble or dispersed in the epoxide resin. R^2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; 3 represents a phenolic hydroxyl group and optionally an m+1 valent group of polyphenol or aminophenol after removal of an amino group, and X represents a group represented by -O- or -NR^2-.) The water-insoluble compound represented. (2) In the above formula I, the group R^3 is the following formula IV: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, Z directly represents a C-C bond, or -CR^6R ^7-, -O-, -S-, -SO_2-,
-CO-, COO-, -CONR^8- and -SiR
represents a bridge selected from the group consisting of ^9yR^1^0-, where R^4 and R^5 each independently represent an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; , represents an alkynyl group having 2 to 6 carbon atoms or a halogen atom, p and q each independently represent 0, 1 or 2, and R^6, R^7 and R^8 each independently represent represents a hydrogen atom, -CF_3 or an alkyl group having 1 to 6 carbon atoms, or R^6 and R^7 together with a common carbon atom represent an alicyclic group having 5 to 12 ring carbon atoms; and R^9 and R^1^0 represent an alkyl group having 1 to 6 carbon atoms. ) The compound according to claim 1, which is derived from bisphenol represented by: (3) In the above formula I, Z is -CH_2-, -C(CF_
3) Represents one selected from the group consisting of_2-, -O-, -SO_2-, direct C-C bond and -C(CH_3)_2-, p and q each represent 0 or 1, and R 3. A compound according to claim 2, wherein ^4 and R^5 represent a C1-C6 alkyl group, a C2-C6 alkenyl group or a C2-6 alkynyl group. (4) The compound according to claim 1, wherein in the above formula I, the group R^3 is derived from a mononuclear aminophenol or a mononuclear polyphenol. (5) substantially free of isocyanate groups and containing at least two free phenolic hydroxyl groups;
and a) a1) is an adduct of the polyisocyanate to a prepolymer polyhydroxyl or polysulfhydryl compound, optionally in combination with a chain extender, or to a mixture of such compounds, or a2) b) reacting a prepolymer polyisocyanate derived from a prepolymer polyether amine with at least one phenol having 2 or 3 phenolic hydroxyl groups or an aminophenol having 1 or 2 phenolic hydroxyl groups; The above formula I can be obtained by
2. The compound according to claim 1, represented by: 6. A compound according to claim 5, wherein component a) is a prepolymer polyisocyanate having an average isocyanate functionality of 2 to 3. 7. A compound according to claim 5, wherein component a1) is an adduct of a polyisocyanate to a hydroxyl-terminated prepolymer having an average molecular weight of 150 to 10,000. (8) A compound according to claim 5, wherein the synthesis component for the preparation of component a1) is a hydroxyl-terminated polyether or polyester. (9) The synthesis component for the production of component a1) is a mixture of hydroxyl-terminated polybutadiene and hydroxyl-terminated polyalkylene glycol or a hydroxyl-terminated polyalkylene glycol having a 1-olefin grafted thereon. 6. A compound according to claim 5. (10) Claim 5 wherein the synthetic component for producing component a1) is a hydroxyl group-terminated polyalkylene glycol.
Compounds described. (11) The following formula V: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R^3, m and n represent the meanings described in claim 1, and r is an integer between 1 and 3. , Y represents a group represented by -O- or -NH-, R^1^3 is an aliphatic group after removing the isocyanate group,
Represents an r+1-valent group of an alicyclic, aromatic or araliphatic polyisocyanate, and R^1^4 represents a polyester group or polyether group at the n-valent hydroxyl group after removing the terminal OH group. represents the index m and the groups R^3 and R^1^3
may be different within a given molecule. ) The compound according to claim 1. (12) In the above formula V, m represents 1 and n is 2 or 3
, r represents 1, Y represents a group represented by -O-, R^1^3 represents a group derived from an aliphatic, alicyclic or aromatic diisocyanate, and R^
12. A compound according to claim 11, wherein 1^4 represents a divalent or trivalent radical of a hydroxyl-terminated polyester or polyether having a molecular weight of 150 to 10,000 after removal of the terminal hydroxyl group. (13) In the above formula V, m represents 1 and n is 2 or 3
, r represents 1, Y represents a group represented by -O-, R^1^3 represents a group derived from an aliphatic or alicyclic diisocyanate, and R^1^4 represents a terminal 150 to 300 after removing hydroxyl groups
12. A compound according to claim 11, which represents a divalent or trivalent radical of a polyalkylene ether polyol having a molecular weight of 0. (14) In the above formula V, n represents 2, and R^1^
4 is the following formula VI: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) (In the formula, s represents 3 or 4, x represents an integer from 5 to 40, and -C_sH_2_s-O- units are given. 14. A compound according to claim 13, which may differ within a given structural unit of formula VI within the definitions given. (15) a) Adducts of substantially equivalent amounts of diisocyanates with mixtures of dihydroxyl-terminated or trihydroxyl-terminated polyethers or polyesters and less than 1% by weight of short-chain diols or triols, based on the hydroxyl-terminated prepolymer. 2. A compound according to claim 1, obtainable by reacting b) with bisphenol or trisphenol in an amount substantially equivalent to the NCO content. (16) The following formula VII: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) (In the formula, R^3, m and n represent the meanings described in claim 1, and Y is -O- or -NH- represents a group represented by, t represents 0 or 1, R^1^5 is an aliphatic group after removing the isocyanate group,
2 of cycloaliphatic, aromatic or araliphatic diisocyanates
and R^1^6 represents an n-valent group of the amino group-terminated polyalkylene ether after removing the terminal NH_2 group. ) The compound according to claim 1. (17) In the above formula VII, m represents 1, n represents 2 or 3, Y represents a group represented by -O-, and R^
1^5 represents a group derived from an aliphatic, cycloaliphatic or aromatic diisocyanate, and R^1^6 is an amino-terminated polyalkylene having a molecular weight of 150 to 10,000 after removal of the terminal amino group. 17. A compound according to claim 16, which represents a divalent or trivalent radical of an ether. (18) In the above formula VII, m represents 1, n represents 2, t represents 0, Y represents a group represented by -O-, and R^1^6 has a molecular weight of 150 to 6000. 17. The compound according to claim 16, which represents a group derived from a divalent amino group-terminated polyalkylene ether having: (19) In the above formula VII, m and t represent 1, n represents 2, R^1^5 represents a divalent group of an aliphatic or alicyclic diisocyanate after removing the isocyanate group, The compound according to claim 16, wherein R^1^6 represents a group derived from a divalent amino group-terminated polyalkylene ether having a molecular weight of 150 to 6,000. (20) At least one compound represented by the following formula IIa: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IIa) and the following formula IIIa: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IIIa) (The above formula In IIa and IIIa, R^1, R^3, X, m
and n have the meanings given in claim 1. ) and at least one compound represented by the above formula IIa.
The free NCO group of the compound represented by
2. A formula according to claim 1, characterized in that the compound of formula IIIa is reacted in such an amount that two groups react per compound of formula IIIa.
A method for producing a compound represented by I. (21) The following formula IIb: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIb) At least one compound represented by the following formula IIIb: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IIIb) (The above formula During IIb and IIIb, R^1, R^2, R^3
, m and n have the meanings given in claim 1, and R
^1^1 represents an alkyl group or an aryl group. ) at least one compound represented by the above formula IIb in such a manner that substantially all free amino groups of the compound represented by the above formula IIb are capped by heating the mixture.
of the above formula I, consisting of initially taking the compounds represented by IIb and IIIb in substantially stoichiometric proportions, or reacting in such a way that the compound represented by the above formula IIIb is present in a slight excess. 2. The method for producing a compound according to claim 1, wherein X represents a group represented by -NR^2-. (22) At least one compound represented by the following formula IIb: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IIb) and the following formula IIIc: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IIIc) (The above formula In IIb and IIIc, R^1, R^2, X and n have the meanings given in claim 1, and R^1^2 has one of the meanings given to R^3 in claim 1. and at least one compound of the formula The above formula IIb
Formulas IIb and
The terminal group of the formula I above consists of initially taking a compound of the formula IIIc in substantially stoichiometric proportions or reacting the compound of the formula IIIc above in a slight excess. A method for producing a compound having an orthophenol group, a periphenol group, or an aminophenol group. (23) A method of using the compound represented by formula I according to claim 1 as a softener for epoxide resins. (24) A composition comprising i) an epoxide compound having at least two 1,2-epoxide groups per molecule and ii) a compound of formula I according to claim 1, or from said components i) and ii). A fusible, but still curable adduct obtainable by heating the composition in a manner known per se. (25) A cured product obtainable by curing the composition according to claim 24.